Organic compounds and their preparation



Patented Jan. 23, 1945 UNITED STATES PATENT OFFICE ORGANIC CODIPOUNDS AND THEIR.

, PREPARATION Kathryn L. Lynch, Stamford, Conn., assignor to American Cyanamid Company, New York. N. Y., a corporation of Maine N Drawing. Application January 14, 1943, Serial No. 472,385

' 12 Claims.

This invention relates to new compounds which have wetting, detergent, dispersing, sudsing and other useful properties. The invention Lncludes the compounds themselves, their methods of preparation, and wetting, emulsifying, demulsifying and detergent compositions containing them.

The compounds of the present invention, the preparation of which will be presently described, may be represented by the general formula and sulfonating the resulting product with an alkaline suliite. The compounds present invention are prepared may be illustrated by means of the following equation in which maleic anhydride is caused to react with methyl N-octadecyl--B-aminopropionate:

The resulting compound is then sulfonated with sodium sulfite as follows:

2 /C1UH81 HC-N N518 0 --0 cmcmc-ocn. 2,5 l

H non-o-om ll l7 ms 0,- -c-N cmcm-c-ocm The condensation reaction is slightly exothermic and proceeds to substantial completion in a short period of time, usually not more than one hour being required. Ordinarily I prefer to o carry out the reaction at a moderate temperato use temperatures ranging from about 10 C. to 120 C. In general, an excess of the amine is to be avoided since the amount in excess of that required to forma monoamide under the conditions of the reaction tends to form a salt with the unreacted acid group of the acid anhydride. I therefore use a slight excess, generally 2 to 5%, of the acid anhydride based upon the theoretical amount necessary to react with the mine.

ture, i. e., 40 to 0., although it is permissible Since it is usually more desirable to conduct the reaction in the liquid phase solvents such as carbon tetrachloride, chloroform, acetone, tertiary butanol, benzene, toluene, dioxane, ethers of suitable boiling points, etc. and other inert solvents may be employed. In such cases the reaction mixture is heated under a reflux condenser at least during the early stages of the reaction. The solvent may later be removed by evaporation.

Among the unsaturated polycarboxylic acid anhydrides which may be employed in my preferred method may be mentionedmaleic anhydride, methyl maleic (citraconic) anhydride, and other alkyl and aryl substituted maleic anhydrides; itaconic, ethylitaconic and isopropylitaconic anhydrides; glutaric anhydride; muconic anhydride; aconitic anhydride; etc.

The reaction product of polycarboxylic a id anhydrides and N-substituted amino propionates disclosed above sulionates with extreme rapidity and ease requiring only a matter of minutes at 80 C. for substantially complete sulfonation. As stated before I use an alkaline suliite although, if desired, the same end may be attained by first neutralizing the free carboxylic acid group of the reaction product of Equation 1 above with an alkaline substance and then sulfonating at the double bond by treatment with an alkaline bisulflte. This latter method is particularly suitable when it is desired that X and X1 be different salt-forming bases.

Although I prefer to prepare my new compounds in the manner outlined above and described in detail in the specific examples they may be prepared by other methods. I may. for example, start with the anhydride of a sulfonated aliphatic polycarboxylic acid such as sulfosuccinic acid, methylsulfosuccinic acid, sulfa-dimethylsuccinic acid, sulfo isopropylsuccinic acid, sulfophenylsuccinic acid, sulfoglutaric acid, sulfomethylgutaric acid, suli'o-octylglutaric acid, sulfopimelic acid, sulfosubaric acid, sulfosebacic acid, suliotricarballylic acid, and the like. These anhydrides of sulfopolycarboxylic acids are reacted with substantially equi-molecular parts of N-substituted amino propionates as described hereinbefore to form sulfo acid monoamides which may then be reacted with a salt formin base to yield the compounds of the present invention.

In most of the specific examples which follow I have employed sodium as the salt-forming radical since sodium sulflte and sodium bisulflte are relatively cheap and easily handled. Also, for most purposes my new compounds are of greatest importance in the form of their sodium salts. For special purposes I may prefer to use my compounds in the term of the acid monoamide in which case both X and X1 in the general formula are hydrogen. My new compounds may be prepared, and are also useful, however, in the form 01' salts in which X and X1 in the general formula are salt-forming radicals such as Na, K, Li, NH4, Ba, Ca, Zn, Cu, Ha, Cd, Mg, Al, etc. or radicals of an amine such as ethanolamine, morpholine, guanidine, pyridine or other hydrophilic saltforming radicals. In order to introduce these radicals into zmr new compounds it is not necessary to use them in the form of sulfites or bisuliites since, if desired, I may prepare the free sulionic acid 01' the polycarboxylic monoamide and neutralize it with a suitable salt-forming base such as one of the class named. Many of these cationic radicals may also be conveniently introduced by means of double decomposition of the sodium salt and desired metal or cationic radical.

In general, the compounds of the present invention are extremely water-soluble, particularly when X, X1, and R2 are alkali metal radicals. In such cases they are water-soluble up to about 50% by weight. Compounds of this type are for the most part ditflcultly soluble in alcohols, ethers, kerosene and other organic solvents. When R2 in the general formula is an alkyl group the com pounds are less water-soluble, about 15 to 25% by weight in water, but are more soluble in organic solvents of the type named. Most of them are colorless pulverable solids. Their aqueous solutions have a pH of about 6.5 to 8.0 depending, of course, upon the nature of the substituted groups. Their solutions possess a high calcium tolerance and show wetting, emulsifying, demulsifying, dispersing, foaming, detergent and other surface active characteristics. They are soluble and stable in strong acid solutions and may be employed in many arts for most purposes for which surface active compounds have been heretofore employed.

The invention will now be described in greater detail by means of the following specific examples. It should be understood that while these examples describe in detail some specific manipulative steps which may be employed in the preparation oi the compounds they are given primarily by way of illustration and the invention in its broader aspects is not to be limited thereto.

Exlmru: 1

N-octadecuLN-(Z-carboethoxuethyl) disodium sulfosuccinamate NaS 0:-

92 g. (0.25 mol) of ethyl N-octadecyl-p-aminopropionate is dissolved in 75 cc. of tertiary butanol and 25 g. (0.25 mol+2% excess) of maleic anhydride is added slowly with stirring while keeping the temperature of the reaction mixture between 60 and 70 C. The reaction is slightly exothermic. The temperature 01 the reaction mixture is held at 65 C. for one-half hour and the solution is then poured into a hot solution of 32.5 g. (0.4 moi-{4% excess) oi sodium sulflte in 200 cc. of water. The maleiamic acid dissolves at once in the sodium sulflte solution to give clear solutions at C. The reaction mixture is held at this temperature for about one hour to insure completion of the reaction. The solvent is then evaporated and the product dried at C. A yield of g. (98% of theory) of N-octadecyl,N- (Z-carboethoxyethyl) disodium suliosuccinamate is obtained. The product is a white waxy solid, soluble in water to give clear solutions having a pH of 6.5. The product is also soluble in kerosene, mineral and vegetable oils.

Chemical analysis of the product shows that it compares well with the theoretical values for N octadecyl,N tz-carboethoxyethyl) disodium sulicsuccinamate. A sample of the product pre- 'aseaoov pared as described above are the'iollowing results upon analysis:

" W *Ji Parent Purcell Theoretical 2. M 01. 5 n. Found 243 08.4 a.

Drove: sinking test at 30 C.

Conc.ingrams per Men... 5 2.5 1.0 0.75 0.5 sinking time in seconds" 32.5 33.5 46.7 80.0 60.8 95

The product is also a very good foaming agent and detergent and has a high resistance to precipitation by calcium and ma nesium ions.

Exnlmmz N-octadeclILN-(2-carbomethosmeth1ll) disodium sulfosuccinamate 0 Ihc-a-ONa 96 g. (0.25 moi) of methyl N-octadecyl-paminopropionate dissolved in 100 cc. of tertiary butanol is added slowly to 25 g. (0.25 mol+2% excess) of maleic anhydride and the mixture heated at 75 C. for minutes to complete the reaction. The reaction mixture is then poured into a hot solution of 32.5 g. (0.25 mol+5% excess) of sodium sulflte in 250 cc. of water. Sulfonation of the maleiamic acid derivative is completed by keeping the solution at 80 to 85 C. for one hour. The solvents are then distilled oil and the product dried at 90 to 95 C. N -octadecyl,N- (2-carbomethoxyethyl) disodium sulfosuccinamate is obtained in theoretical yields as a creamcolored solid. It is soluble in water to give clear, strongly foaming solutions having a pH of 6.5. It is an excellent detergent, roaming, emulsifying and dispersing agent.

Chemical analysis of a product obtained by the process of the preceding paragraph checked closely with the theoretical values for N-ootadecyl,N-(2-carbomethoxyethyl) disodium suli'osuccinamate.

The N-dodecyl, N-tetradecyl, N-hendecyl and N-octadecenylfl-Q-cerboalkoxyethyi) dioodium sultosuocinamates are prepared in exactly the samewayasdescribedintheprecedingexamples with the exception that the compounding N- alkyl-p-amino-propionate ester is employed in.

The dodecyl.

molecular equivalent quantities. and tetradecyi derivatives are better wetting agents than the octadecyl N-carboalkoxyethyl dlsodium suliosuccinamates but not quite so emclent as detergents. Potassium or ammonium salts are prepared by substituting potassium or ammonium suliite for sodium suliite. The properties of the resulting compounds are altered but little as a result 01 the substitution.

Exmu4 N-octodeculfl-(Z-Mrbozyethpl) trisodium salieruccmomote O Hill-ON! all:

91 g. (0.25 moi) of sodium N-octadecyl-pamino-propionate is dissolved in 100 cc. terltiary butanol and 25 g. (0.25 mol+2% excess) of maleic anhydride is added and the mixture heated on a steam. bath at C. for 15 minutes after which is added 32.5 g. of sodium sulflte dissolved in 250 cc. of hot water. The solution is held at to 00 C. for 15 hours to insure complete sulfonation and then dried by evaporating oil the solvents. A yield of g. of a, white pulverable solid, very readily soluble in water to give clear, strongly foaming solutions of pH of 7.0 to 1.5; is obtained. The product, N-octadecylN-(Z-carbonethyl) trisodium suliosuccinamate is an excellent detergent and dispersing ent.

Chemical analysis of a sample oi the product compared favorably with the theoretical analysis for N-octadecylJl-(Z-carboxyethyl) trisodium suliosuccinamate as shown by the following re- N-octadecylN-(Z-carboxyethyl) trisodium sulfosuccinamate, described in the preceding example may also be prepared by heating one mol of N-octadecylN-Q-carboethoxyethyl) disodlum suli'osuccinamate prepared as described in Example 1 with one moi of sodium hydroxide at25to00'C.lnaqueoussolution. Inthisproc- XBOr-B R1 CHgCHg-C-O E:

in which X and K1 are members of the group consisting of hydrogen and cationic salt-forming radicals, R is the residue of an aliphatic polycarboiwlic acid, R1 is an alkyl radical having from 8 to 20 carbon atoms inclusive, and R: is a member of the group consisting of hydrogen, cationic salt-forming radicals and alkyl radicals having 1 to carbon atoms inclusive.

2. Organic compounds having the general formula cmcm-c-o R1 in which x and X: are members of the group consisting of hydrogen and cationic salt-forming radicals, R1 is an alkyl radical having from B to 20 carbon atoms inclusive, and R2 is a member of the group consisting of hydrogen, cationic salt-forming radicals and alkyl radicals having 1 to 5 carbon atoms inclusive.

3. Organic compounds having the general formula in which X and K1 are alkali metals, R1 is an alkyl radical having from 8 to 20 carbon atoms inclusive, and R: is an alkyl radical having from 1 to 5 carbon atoms inclusive.

4. N-octadecyl,N-(Z-carboethoxyethyl) disodium suliosuccinamate.

5. N-octadecyLN-(Z-carbomethoxyethyl) disodium sulfosuccinamate.

6. N-octadecyl,N- (ll-carboxyethyi) sulfosuccinamate.

trisodium assault:

7. A process of preparing compounds having the general formula in which X and K1 are members of the group consisting of hydrogen and cationic salt-forming radicals, R is the residue of an aliphatic polycarboxylic acid, R1 is an alkyl radical having from 8 to 20 carbon atoms inclusive. and R2 is a member of the group consisting of hydrogen, cationic salt-forming radicals and alkyl radicals having 1 to 5 carbon atoms inclusive, which comprises reacting an anhydride of an unsaturated aliphatic polycarboxylic acid with a compound having the general formula o R NHCH1CH!- 0Bi in which R1 and R2 are as designated above and sulfonating the resulting product with an alkaline sulflte.

8. A method of preparing compounds of the general formula in which X and K1 are members of the group consisting of hydrogen and cationic salt-forming radicals, and R1 is an alkyl radical having from 8 to 20 carbon atoms inclusive, and R4 is a member of the group consisting of hydrogen,

cationic salt-forming radicals and alkyl radicals having 1 to 5 carbon atoms inclusive, which comprises reacting maleic anhydride with compounds having the general formula in which R1 and R2 are as designated above and sulfonating the resulting product with an alkaline sulfite.

9. A method of preparing organic compounds having the general formula in which x and K1 are alkali metals, R1 is an alkyl radical having from 2 to 12 carbon atoms inclusive, and R2 is an alkyl radical having from 1 to 5 carbon atoms inclusive, which comprises reacting maleic anhydride with compounds having the general formula in which R1 and R: are as designated above and sgllfflotreiating the resulting product with an alkali s mamethodolwepatlnlorzanicoompounds having the moral formula 0 B c-LON- which R1 is an alkyl radical having from 8 Mcarhmatmnsinclusiveandflflsan alkyl havingtmml to5carbonatomsincluwhicheomwiseereactingmaleic anhydride luring the general formula 0 HIE-OHICHa-E OK in which R; and R: are as designated above and suiionating the resulting product with sodium sulflte.

11. A method of preparing N-octadecyi,N-(2- CERTIFICATE OF CORRECTI ON.

Patent I0. 2,568,067-

J'anuary 25, 19 45.

KATHRYN L. LYNCH- It is hereby certified that error appears in the printed specification oftheahove numbered patent requiring correction as follows: Page 3, secand colon, line 57, for "15 hours read --1.5 hours; page LL, second coluun, line 64., claim 9, for "2 to 12 carbon atoms read --8 to 20 carbon atom--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Offl ce Signed and use this aim; day or April, A. D. 191.5.

(Seal) Leslie Frazer Acting Commissioner of Patents.

mamethodolwepatlnlorzanicoompounds having the moral formula 0 B c-LON- which R1 is an alkyl radical having from 8 Mcarhmatmnsinclusiveandflflsan alkyl havingtmml to5carbonatomsincluwhicheomwiseereactingmaleic anhydride luring the general formula 0 HIE-OHICHa-E OK in which R; and R: are as designated above and suiionating the resulting product with sodium sulflte.

11. A method of preparing N-octadecyi,N-(2- CERTIFICATE OF CORRECTI ON.

Patent I0. 2,568,067-

J'anuary 25, 19 45.

KATHRYN L. LYNCH- It is hereby certified that error appears in the printed specification oftheahove numbered patent requiring correction as follows: Page 3, secand colon, line 57, for "15 hours read --1.5 hours; page LL, second coluun, line 64., claim 9, for "2 to 12 carbon atoms read --8 to 20 carbon atom--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Offl ce Signed and use this aim; day or April, A. D. 191.5.

(Seal) Leslie Frazer Acting Commissioner of Patents. 

